CN109761824A - A kind of method of Catalytic Hydrqenation for Synthesis of p minphenol coproduction p-aminophenyl ether - Google Patents
A kind of method of Catalytic Hydrqenation for Synthesis of p minphenol coproduction p-aminophenyl ether Download PDFInfo
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Abstract
The invention belongs to the technical fields of organic chemical industry, it is related to a kind of method of Catalytic Hydrqenation for Synthesis of p minphenol coproduction high added value p-aminophenyl ether, more specifically, it is related to one kind using nitrobenzene, alcohol as raw material, para-aminophenol and p-aminophenyl ether are prepared through catalytic hydrogenation and rearrangement in acid medium, nitrobenzene conversion rate >=99.5%, para-aminophenol and 85% or more p-aminophenyl ether total recovery.The present invention has many advantages, such as that raw material is cheap and easy to get, production process is few, wastewater flow rate is easy to handle less, pollution is small, while can be suitable for industrialized production according to the ratio and technique change that nitrobenzene and alcohol is added come the ratio of two kinds of products of any adjustment.
Description
Technical field
The invention belongs to the technical fields of organic chemical industry, and it is additional to be related to a kind of Catalytic Hydrqenation for Synthesis of p minphenol coproduction height
It is worth the method for p-aminophenyl ether, more particularly, to one kind using nitrobenzene, alcohol as raw material, through catalytic hydrogenation in acid medium
And rearrangement prepares para-aminophenol and p-aminophenyl ether, nitrobenzene conversion rate >=99.5%, para-aminophenol and p-aminophenyl ether
85% or more total recovery.The present invention has many advantages, such as that raw material is cheap and easy to get, production process is few, wastewater flow rate is easy to handle less, pollution is small,
It can be suitable for work according to the ratio and technique change that nitrobenzene and alcohol is added come the ratio of two kinds of products of any adjustment simultaneously
Industry metaplasia produces.
Background technique
Para-aminophenol (abbreviation PAP) is a kind of widely used organic synthesis intermediate, is widely used in medicine and (flutters heat
Cease pain, clofibrate vitamin B1, complexing agent niacinamide, 6- oxyquinoline etc.), dyestuff, rubber, the fields such as photograph.P-aminophenyl
Ether is the important intermediate for producing dyestuff, medicine and fragrance etc., such as paraphenetidine, para aminophenyl ethyl ether.To ammonia
Base phenetole is commonly used for producing C.I. Blue VRS 9,83,90 etc., C.I. alkali blue 18, C.I. disperse yellow 34,86, C.I. face
Expect red 123 equal dyestuffs；Pharmaceutically for producing celiprolol, phenaetin, acthoxide and rivanol etc.；Also it is used as ageing of rubber
The precursor of protective agent, food or feed anticorrosion agent, antioxidant is widely used.
There are many domestic and international report in relation to para-aminophenol, p-aminophenyl ether study on the synthesis, and main production process has: to chlorine
Nitrobenzene method and nitrobenzene method.Parachloronitrobenzene method is using paranitrochlorobenzene as raw material, and paranitrochlorobenzene adds under alkaline condition
Pressure hydrolysis obtains paranitrophenol sodium salt, then para-aminophenol is made in acidified and reduction；Or paranitrochlorobenzene and first/ethyl alcohol, alkali
Liquid carries out alkoxylation and generates p-nitrophenyl ether, then obtains p-aminophenyl ether through reduction.Parachloronitrobenzene method is to amino
Occupy the superiority of technology maturation in phenol, the production of p-aminophenyl ether, but there are synthetic routes longer, high production cost, dirt
Contaminate the problems such as serious.Hydrogenation of chloronitrobenzene reduction method prepares para-aminophenol with raw material is cheap and easy to get, production process is few, product matter
It measures, pollute the advantages that small, " three wastes " are easily handled, be an environmentally friendly, competitive process route；But openly
Report that the document of nitrobenzene method synthesis p-aminophenyl ether is seldom.
Patent US2198249 (1940) makes public for the first time in the presence of Pt/C catalyst, inorganic acid through hydrogenation of chloronitrobenzene
Para-aminophenol is made, reports many correlative study technologies successively later.Patent US4885389A is disclosed to be urged in 3% Pt/C
In the presence of agent, it is situated between using containing 0.1~1% sulfuric acid solution of organic acid (formic acid, acetic acid, trichloroacetic acid etc.) as reaction
Matter, nitrobenzene prepare para-aminophenol in 60-100 DEG C plus hydrogen, and product yield reaches 83%.Patent US6403833 is disclosed
In sulfuric acid medium, a series of list Ni catalyst and compound Ni-Pd and Ni-Pt catalyst are applied to hydrogenation of chloronitrobenzene preparation pair
Amino-phenol, reaction temperature are 120 DEG C, and the selectivity of para-aminophenol is up to 65%.Tanielyan, Wang Dingjun et al. are ground
Study carefully and has done phase turn in 80~90 DEG C, lower pressure, 1.5%Pt/C catalyst, sulfuric acid concentration 10~15%, addition surfactant
Under the conditions of shifting catalyst, hydrogenation of chloronitrobenzene prepares para-aminophenol and obtains preferable result (PAP/AN=6.7mol).Patent
CN10440040, which is disclosed, to be supported on solid acid with Pt metal as catalyst, in neutral or slightly acidic water solution, from nitro
Benzene catalytic hydrogenation prepares para-aminophenol, and product yield is up to 17~83%；It solves and synthesizes from Catalytic Hydrogenation of Nitrobenzene to amino
Phenol process is existing using sulfuric acid as reaction medium, and corrosivity is strong, requires high, a large amount of dilute ammonium sulfate solutions of by-product to equipment material
The problems such as handling.
Gao Lei et al. is mentioned in " research of paraphenetidine technology ", and nitrobenzene is sub- in sulfuric acid-methanol and diformazan
Alum be solvent, using noble metal as catalyst, hydrogen pressure paraphenetidine can be made, severe reaction conditions use higher boiling water
Solubleness organic solvent, separation is difficult, and subsequent processing is complicated, causes environmental pollution.
Above-mentioned is all the method for preparing para-aminophenol or p-aminophenyl ether as primary raw material using nitrobenzene, but because reacting work
The difference of skill or reaction system, all can only production list one product；It is of the invention to focus on through a set of reaction unit, one pot
Method synthesizes two kinds of products of para-aminophenol and p-aminophenyl ether, in the process according to the ratio and work that raw material nitrobenzene and alcohol is added
Skill variation carrys out the ratio of two kinds of products of any adjustment, adapts to demand of the market to product, is suitable for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of Catalytic Hydrqenation for Synthesis of p minphenol coproduction high added value p-aminophenyl ethers
Method, more particularly, to one kind using nitrobenzene, alcohol as raw material, through catalytic hydrogenation and rearrangement preparation to ammonia in acid medium
Base phenol and p-aminophenyl ether, nitrobenzene conversion rate >=99.5%, para-aminophenol and 85% or more p-aminophenyl ether total recovery.
The present invention have many advantages, such as raw material is cheap and easy to get, production process is few, wastewater flow rate it is few it is easy to handle, pollution is small, while can be according to adding
The ratio and technique change that enter nitrobenzene and alcohol carry out the ratio of two kinds of products of any adjustment, adapt to demand of the market to product,
It is suitable for industrialized production.
The present invention provides a kind of method of Catalytic Hydrqenation for Synthesis of p minphenol coproduction high added value p-aminophenyl ether, the party
Method includes the following steps:
Pt/C catalyst, nitrobenzene, alcohol, phase transfer catalyst and dilute sulfuric acid are put into autoclave, logical nitrogen is set
It ventilates 5 times or more, is passed through hydrogen to hydrogen partial pressure 0.1kgf~10kgf, then opens stirring and be warming up to 60~110 DEG C of reactions 1
~10hr；Reaction terminates, and is down to room temperature suction filtration, and recycling catalyst cake is recycled after being washed with deionized, filtrate liquid
Alkali or ammonium hydroxide adjust pH=7~7.5, and unreacted methanol and by-product aniline are recycled in air-distillation, until aniline content in kettle liquid
≤ 0.1%；Distillation kettle liquid slow cooling is precipitated crystal to≤0 DEG C, is filtered, and the mixed of para-aminophenol and p-aminophenyl ether is obtained
Product is closed, mix products are obtained into p-aminophenyl ether product, rectifying still material weight in organic or inorganic medium by rectification under vacuum
Crystallization obtains p-aminophenyl phenolic product.
In above-mentioned steps (1), the alcohol is methanol, ethyl alcohol, normal propyl alcohol, isopropanol and n-butanol, preferably methanol and ethyl alcohol.
In above-mentioned steps (1), the preferred 0.2kgf~6kgf of hydrogen partial pressure, more excellent 0.5kgf~4kgf.
In above-mentioned steps (1), preferably 65~95 DEG C of the reaction temperature.
In above-mentioned steps (1), the reaction time preferably 2~6hr.
In above-mentioned steps (1), Pt metal content 0.5~5% in the Pt/C catalyst, preferably 1~3%Pt/C catalysis
Agent.
In above-mentioned steps (1), the Pt/C catalyst amount is 0.2~8%, preferably the 0.5~5% of nitrobenzene weight.
In above-mentioned steps (1), the phase transfer catalyst be quaternary ammonium salt and PEG, such as cetyl trimethylammonium bromide,
Dodecyl trimethyl ammonium bromide, hexadecyltrimethylammonium chloride, dodecyl trimethyl ammonium chloride, PEG400, PEG600
Etc., phase transfer catalyst dosage accounts for nitrobenzene amount 0.3~5%, preferably 0.5~1%.
In above-mentioned steps (1), the dilute sulfuric acid concentration is 5~30%, preferably 10~20%.
In above-mentioned steps (1), the molar ratio of the nitrobenzene and alcohol is 1:0~10, preferably 0.5~2.5.
In above-mentioned steps (1), the molar ratio of the nitrobenzene and sulfuric acid is 1:0.5~2, preferably 0.9~1.2.
In above-mentioned steps (3), the recrystallization medium is one of water, methanol, ethyl alcohol or a variety of mixtures.
The present invention is with nitrobenzene, methanol (or ethyl alcohol) and acid for raw material, and nitrobenzene elder generation catalytic hydrogenating reduction generates phenyl
Then azanol is reset in acid medium and generates para-aminophenol and p-aminophenyl ether；Reaction equation is as follows:
The present invention is to overcome disadvantage present in existing synthetic method, using a kind of raw material is cheap and easy to get, production process is few,
The method of small synthesis para-aminophenol coproduction high added value p-aminophenyl ether is polluted, the method achieve in a set of reaction unit
Upper, two kinds of products of one pot process para-aminophenol and p-aminophenyl ether, nitrobenzene conversion rate >=99.5%, para-aminophenol and
85% or more p-aminophenyl ether total recovery；Demand according to market to two kinds of products, raw material is added in appropriate adjustment in production process
The ratio or process conditions of nitrobenzene and alcohol meet throughput requirements, and raw material nitrobenzene ratio increase is conducive to improve p-aminophenyl
Phenol yield, material benzenemethanol or proportion of ethanol increase are conducive to improve p-aminophenyl ether yield, improve hydrogen pressure or extend the reaction time
It is also beneficial to improve p-aminophenyl ether yield, technical process control is easy flexibly, is suitable for industrialized production.
Specific embodiment
Embodiment 1
Nitrobenzene 75g, 15% sulfuric acid 478g, methanol 10g, 2%Pt/C catalyst are added in 1L autoclave
0.75g, cetyl trimethylammonium bromide 0.75g lead to nitrogen displaced air 6 times, are passed through hydrogen to hydrogen partial pressure 2kgf, then
Opening stirring and being warming up to 90 DEG C of reaction 2hr terminates, and cools down, filters, and recycles catalyst wet basis 0.8g, and hydrogen filtrate is added to utilize liquid chromatogram
Para-aminophenol yield 76%, paraphenetidine yield 15.5%, by-product aniline yield rate 6% are known in analysis.
Filtrate adjusts pH=7~7.5 with 25% ammonium hydroxide, and unreacted methanol and by-product aniline are recycled in air-distillation, point
Aniline content 0.05% in kettle liquid is analysed to stop；Distillation kettle liquid slow cooling is precipitated crystal to≤0 DEG C, is filtered, is obtained p-aminophenyl
Mix products are obtained paraphenetidine product 11.3g by rectification under vacuum by the mix products of phenol and paraphenetidine, right
Aminoanisole yield 15%；Rectifying still material is recrystallized to give p-aminophenyl phenolic product 50.5g in 50% methanol aqueous solution,
PAP yield 75.2%.
Embodiment 2
Nitrobenzene 75g, 15% sulfuric acid 398.4g, methanol 40g, 2%Pt/C catalyst are added in 1L autoclave
0.75g, cetyl trimethylammonium bromide 0.4g lead to nitrogen displaced air 6 times, are passed through hydrogen to hydrogen partial pressure 2kgf, then
Opening stirring and being warming up to 80 DEG C of reaction 4hr terminates, and cools down, filters, and recycles catalyst wet basis 0.8g, and hydrogen filtrate is added to utilize liquid chromatogram
Para-aminophenol yield 17%, paraphenetidine yield 74.5%, by-product aniline yield rate 5% are known in analysis.
Filtrate adjusts pH=7~7.5 with 30% sodium hydroxide, and unreacted methanol and by-product benzene are recycled in air-distillation
Amine is analyzed aniline content 0.04% in kettle liquid and is stopped；Distillation kettle liquid slow cooling is precipitated crystal to≤0 DEG C, is filtered, and is obtained pair
Mix products are obtained paraphenetidine product by rectification under vacuum by the mix products of amino-phenol and paraphenetidine
55.8g, paraphenetidine yield 73.9%；Rectifying still material is recrystallized to give para-aminophenol production in 60% methanol aqueous solution
Product 11.1g, PAP yield 16.5%.
Embodiment 3
In 1L autoclave be added nitrobenzene 75g, 10% sulfuric acid 597.6g, methanol 20g, 1%Pt/C catalyst 3g,
Dodecyl trimethyl ammonium bromide 0.55g leads to nitrogen displaced air 6 times, is passed through hydrogen to hydrogen partial pressure 4kgf, then opens stirring
Being warming up to 65 DEG C of reaction 5hr terminates, and cools down, filters, and recycles catalyst wet basis 3.2g, hydrogen filtrate is added to know using liquid-phase chromatographic analysis
Para-aminophenol yield 51.6%, paraphenetidine yield 42.5%, by-product aniline yield rate 4.5%.
Filtrate adjusts pH=7~7.5 with 30% ammonium hydroxide, and unreacted methanol and by-product aniline are recycled in air-distillation, point
Aniline content 0.068% in kettle liquid is analysed to stop；Distillation kettle liquid slow cooling is precipitated crystal to≤0 DEG C, is filtered, is obtained to amino
Mix products are obtained paraphenetidine product 31.8g by rectification under vacuum by the mix products of phenol and paraphenetidine,
Paraphenetidine yield 42%；Rectifying still material is recrystallized to give p-aminophenyl phenolic product 34.3g in 50% methanol aqueous solution,
PAP yield 51.1%.
Embodiment 4
Nitrobenzene 90g, 20% sulfuric acid 376.5g, methanol 48.8g, 3%Pt/C catalyst are added in 1L autoclave
3g, dodecyl trimethyl ammonium bromide 0.72g lead to nitrogen displaced air 6 times, are passed through hydrogen to hydrogen partial pressure 3kgf, then open
Stirring, which is warming up to 85 DEG C of reaction 3.5hr, to be terminated, and is cooled down, is filtered, and catalyst wet basis 3.15g is recycled, and hydrogen filtrate is added to utilize liquid phase color
Spectrum analysis knows para-aminophenol yield 8.9%, paraphenetidine yield 80.5%, by-product aniline yield rate 8.8%.
Filtrate adjusts pH=7~7.5 with 20% ammonium hydroxide, and unreacted methanol and by-product aniline are recycled in air-distillation, point
Aniline content 0.08% in kettle liquid is analysed to stop；Distillation kettle liquid slow cooling is precipitated crystal to≤0 DEG C, is filtered, is obtained p-aminophenyl
Mix products are obtained paraphenetidine product 72.5g by rectification under vacuum by the mix products of phenol and paraphenetidine, right
Aminoanisole yield 80.1%；Rectifying still material is recrystallized to give p-aminophenyl phenolic product 6.3g in 50% methanol aqueous solution,
PAP yield 7.8%.
Embodiment 5
Nitrobenzene 90g, 20% sulfuric acid 394.4g, methanol 48.8g, 3%Pt/C catalyst are added in 1L autoclave
0.5g, PEG400 0.9g lead to nitrogen displaced air 6 times, are passed through hydrogen to hydrogen partial pressure 3kgf, then open stirring and be warming up to 75
DEG C reaction 6hr terminate, cool down, filter, recycle catalyst wet basis 0.55g, add hydrogen filtrate to know using liquid-phase chromatographic analysis to amino
Phenol yield 8.5%, paraphenetidine yield 78.5%, by-product aniline yield rate 10.8%.
Filtrate adjusts pH=7~7.5 with 25% ammonium hydroxide, and unreacted methanol and by-product aniline are recycled in air-distillation, point
Aniline content 0.08% in kettle liquid is analysed to stop；Distillation kettle liquid slow cooling is precipitated crystal to≤0 DEG C, is filtered, is obtained p-aminophenyl
Mix products are obtained paraphenetidine product 70.6g by rectification under vacuum by the mix products of phenol and paraphenetidine, right
Aminoanisole yield 78.1%；Rectifying still material is recrystallized to give p-aminophenyl phenolic product 6.3g in 20% methanol aqueous solution,
PAP yield 7.8%.
Embodiment 6
Nitrobenzene 75g, 10% sulfuric acid 657.3g, methanol 10g, 1%Pt/C catalyst are added in 1L autoclave
1.5g, PEG600 0.75g lead to nitrogen displaced air 6 times, are passed through hydrogen to hydrogen partial pressure 2kgf, then open stirring and be warming up to 85
DEG C reaction 4.5hr terminate, cool down, filter, recycle catalyst wet basis 1.6g, add hydrogen filtrate to know using liquid-phase chromatographic analysis to amino
Phenol yield 78.5%, paraphenetidine yield 8.5%, by-product aniline yield rate 10.8%.
Filtrate adjusts pH=7~7.5 with 30% ammonium hydroxide, and unreacted methanol and by-product aniline are recycled in air-distillation, point
Aniline content 0.05% in kettle liquid is analysed to stop；Distillation kettle liquid slow cooling is precipitated crystal to≤0 DEG C, is filtered, is obtained p-aminophenyl
Mix products are obtained paraphenetidine product 6.1g by rectification under vacuum by the mix products of phenol and paraphenetidine, right
Aminoanisole yield 8.1%；Rectifying still material is recrystallized to give p-aminophenyl phenolic product 52g, PAP in 20% methanol aqueous solution
Yield 77.9%.
Embodiment 7
Nitrobenzene 75g is added in 1L autoclave, 10% sulfuric acid 657.3g, methanol 10g, applies the recycling of embodiment 6
Catalyst adds raw catelyst 0.5%wt, hexadecyltrimethylammonium chloride 0.75g, leads to nitrogen displaced air 6 times, is passed through hydrogen
To hydrogen partial pressure 2kgf, then opening stirring and being warming up to 85 DEG C of reaction 4.7hr terminates gas, cools down, filters, recycles catalyst wet basis
1.63g adds hydrogen filtrate to know para-aminophenol yield 78.3%, paraphenetidine yield 8.2%, pair using liquid-phase chromatographic analysis
Produce aniline yield rate 11.0%.
Filtrate adjusts pH=7~7.5 with 30% ammonium hydroxide, and unreacted methanol and by-product aniline are recycled in air-distillation, point
Aniline content 0.05% in kettle liquid is analysed to stop；Distillation kettle liquid slow cooling is precipitated crystal to≤0 DEG C, is filtered, is obtained p-aminophenyl
Mix products are obtained paraphenetidine product 5.9g by rectification under vacuum by the mix products of phenol and paraphenetidine, right
Aminoanisole yield 7.83%；Rectifying still material is recrystallized to give p-aminophenyl phenolic product 51.8g in 20% methanol aqueous solution,
PAP yield 77.5%.
Embodiment 8-13
Process conditions and operating process all substitute methanol used successively with embodiment 1-6 with ethyl alcohol.Acquired results are as follows
Shown in table:
Content of the present invention is not limited in embodiment content of the present invention.
Specific case used herein is expounded structure of the invention and embodiment, and the foregoing is merely this hairs
Bright preferred embodiment and oneself, be not intended to limit the invention, it is all within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method of Catalytic Hydrqenation for Synthesis of p minphenol coproduction p-aminophenyl ether, which is characterized in that this method includes such as
Lower step:
Pt/C catalyst, nitrobenzene, alcohol, phase transfer catalyst and dilute sulfuric acid are put into autoclave by step (1), lead to nitrogen
Displaced air 5 times or more, hydrogen is passed through to hydrogen partial pressure 0.1kgf~10kgf, stirring is then opened and is warming up to 60~110 DEG C of reactions
1~10hr；
Step (2) reaction terminates, and is down to room temperature suction filtration, and recycling catalyst cake is recycled after being washed with deionized, filtrate
PH=7~7.5 are adjusted with liquid alkaline or ammonium hydroxide, unreacted methanol and by-product aniline are recycled in air-distillation, until aniline in kettle liquid
Content≤0.1%；
Step (3) distillation kettle liquid slow cooling is precipitated crystal to≤0 DEG C, is filtered, and para-aminophenol and p-aminophenyl ether are obtained
Mix products are obtained p-aminophenyl ether product by rectification under vacuum by mix products, and rectifying still material is in organic or inorganic medium
It is recrystallized to give p-aminophenyl phenolic product.
2. the method for Catalytic Hydrqenation for Synthesis of p minphenol coproduction p-aminophenyl ether according to claim 1, feature exist
In in above-mentioned steps (1), the alcohol is methanol, ethyl alcohol, normal propyl alcohol, isopropanol and n-butanol, preferably methanol and ethyl alcohol.
3. the method for Catalytic Hydrqenation for Synthesis of p minphenol coproduction p-aminophenyl ether according to claim 1, feature exist
In in above-mentioned steps (1), the hydrogen partial pressure is 0.2kgf~6kgf, preferably 0.5kgf~4kgf.
4. the method for Catalytic Hydrqenation for Synthesis of p minphenol coproduction high added value p-aminophenyl ether according to claim 1,
It is characterized in that, the reaction temperature is 65~95 DEG C in above-mentioned steps (1).
5. the method for Catalytic Hydrqenation for Synthesis of p minphenol coproduction high added value p-aminophenyl ether according to claim 1,
It is characterized in that, the reaction time is 2~6hr in above-mentioned steps (1).
6. the method for Catalytic Hydrqenation for Synthesis of p minphenol coproduction high added value p-aminophenyl ether according to claim 1,
It is characterized in that, in above-mentioned steps (1), Pt metal 0.5~5wt% of content, preferably 1~3wt%Pt/ in the Pt/C catalyst
C catalyst；The Pt/C catalyst amount is the 0.2~8wt%, preferably 0.5~5wt% of nitrobenzene weight.
7. the method for Catalytic Hydrqenation for Synthesis of p minphenol coproduction high added value p-aminophenyl ether according to claim 1,
It is characterized in that, the dilute sulfuric acid concentration is 5~30wt%, preferably 10~20wt% in above-mentioned steps (1).
8. the method for Catalytic Hydrqenation for Synthesis of p minphenol coproduction high added value p-aminophenyl ether according to claim 1,
It is characterized in that, the phase transfer catalyst is quaternary ammonium salt and PEG, preferably cetyl trimethyl bromination in above-mentioned steps (1)
Ammonium, dodecyl trimethyl ammonium bromide, hexadecyltrimethylammonium chloride, dodecyl trimethyl ammonium chloride, PEG400,
PEG600, phase transfer catalyst dosage account for nitrobenzene 0.3~5wt% of amount, preferably 0.5~1wt%.
9. the method for Catalytic Hydrqenation for Synthesis of p minphenol coproduction high added value p-aminophenyl ether according to claim 1,
It is characterized in that, in above-mentioned steps (1), the molar ratio of the nitrobenzene and alcohol is 1:0~10, preferably 0.5~2.5；The nitre
The molar ratio of base benzene and sulfuric acid be 1:0.5~2, preferably 0.9~1.2.
10. the method for Catalytic Hydrqenation for Synthesis of p minphenol coproduction high added value p-aminophenyl ether according to claim 1,
It is characterized in that, the recrystallization medium is one of water, methanol, ethyl alcohol or a variety of mixtures in above-mentioned steps (3).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112812025A (en) * | 2021-01-13 | 2021-05-18 | 江苏普洛德化学科技有限公司 | Preparation process of p-aminophenol |
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